ACS Organic & Inorganic Au最新文献_第3页

Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-11 DOI: 10.1021/acsorginorgau.4c0004610.1021/acsorginorgau.4c00046

Mahika Luthra, Abril C. Castro*, David Balcells, Kim Daasbjerg and Ainara Nova*,

{"title":"Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study","authors":"Mahika Luthra, Abril C. Castro*, David Balcells, Kim Daasbjerg and Ainara Nova*, ","doi":"10.1021/acsorginorgau.4c0004610.1021/acsorginorgau.4c00046","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00046https://doi.org/10.1021/acsorginorgau.4c00046","url":null,"abstract":"In this study, the electrocatalytic reduction of carbon dioxide by MnI, ReI, and RuII bipyridine complexes bearing pendant amines is evaluated by DFT methods. Prior experimental studies showed that introducing pendant amines in the secondary coordination sphere of the catalyst shifts product selectivity from CO to HCOO– (in the presence of a proton source) in the case of Mn. In contrast, CO is the major product with Re and Ru. This work includes a comprehensive study of the pathways leading to CO, HCOO–, and H2 to elucidate the energetic preferences that underlie product selectivity. Our results show that switching the metal center leads to changes in the preferred mechanism. While with Mn, the reaction is preferred in an endo configuration, allowing the participation of amines in the hydride formation, reactivity on the exo configuration is preferred with Re. In addition, the distinct redox properties of Re allow for the formation of Re OCOCO2-bridged adducts that lead to CO without a proton source. Further, the ability of Ru to exchange the two Cl– anions changes the preferred coordination number of Ru compared to Mn and Re and, consequently, its reaction mechanism. Overall, this study provides the structure and reactivity insight needed for further catalyst design.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"26–36 26–36"},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO₂ by Bipyridine Complexes Bearing Pendant Amines: A DFT Study.

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-11 eCollection Date: 2025-02-05 DOI: 10.1021/acsorginorgau.4c00046

Mahika Luthra, Abril C Castro, David Balcells, Kim Daasbjerg, Ainara Nova

{"title":"Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study.","authors":"Mahika Luthra, Abril C Castro, David Balcells, Kim Daasbjerg, Ainara Nova","doi":"10.1021/acsorginorgau.4c00046","DOIUrl":"10.1021/acsorginorgau.4c00046","url":null,"abstract":"In this study, the electrocatalytic reduction of carbon dioxide by MnI, ReI, and RuII bipyridine complexes bearing pendant amines is evaluated by DFT methods. Prior experimental studies showed that introducing pendant amines in the secondary coordination sphere of the catalyst shifts product selectivity from CO to HCOO- (in the presence of a proton source) in the case of Mn. In contrast, CO is the major product with Re and Ru. This work includes a comprehensive study of the pathways leading to CO, HCOO-, and H2 to elucidate the energetic preferences that underlie product selectivity. Our results show that switching the metal center leads to changes in the preferred mechanism. While with Mn, the reaction is preferred in an endo configuration, allowing the participation of amines in the hydride formation, reactivity on the exo configuration is preferred with Re. In addition, the distinct redox properties of Re allow for the formation of Re OCOCO2-bridged adducts that lead to CO without a proton source. Further, the ability of Ru to exchange the two Cl- anions changes the preferred coordination number of Ru compared to Mn and Re and, consequently, its reaction mechanism. Overall, this study provides the structure and reactivity insight needed for further catalyst design.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"26-36"},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803466/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2 催化剂质子化改变了电化学氢化物向CO2转移的机理

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-04 DOI: 10.1021/acsorginorgau.4c0004110.1021/acsorginorgau.4c00041

Kevin Y. C. Lee, Dmitry E. Polyansky, David C. Grills, James C. Fettinger, Marcos Aceves and Louise A. Berben*,

{"title":"Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2","authors":"Kevin Y. C. Lee, Dmitry E. Polyansky, David C. Grills, James C. Fettinger, Marcos Aceves and Louise A. Berben*, ","doi":"10.1021/acsorginorgau.4c0004110.1021/acsorginorgau.4c00041","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00041https://doi.org/10.1021/acsorginorgau.4c00041","url":null,"abstract":"It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemically driven hydride transfer (HT) catalysis. Protonated, air-stable [HFe4N(triethyl phosphine (PEt3))4(CO)8] (H4) was synthesized by reaction of PEt3 with [Fe4N(CO)12]− (A–) in tetrahydrofuran, with addition of benzoic acid to the reaction mixture. The reduction potential of H4 is −1.70 V vs SCE which is 350 mV anodic of the reduction potential for 4–. Reactivity studies are consistent with HT to CO2 or to H+ (carbonic acid), as the chemical event following ET, when the electrocatalysis is performed under 1 atm of CO2 or N2, respectively. Taken together, the chemical and electrochemical studies of mechanism suggest an ECEC mechanism for the reduction of CO2 to formate or H+ to H2, promoted by H4. This stands in contrast to an ET, two chemical steps, followed by an ET (ECCE) mechanism that is promoted by the less electron rich catalyst A–, since A– must be reduced to A2– before HA– can be accessed.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"649–657 649–657"},"PeriodicalIF":3.3,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO₂. 催化剂质子化改变了电化学氢化物向CO2转移的机理。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-04 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00041

Kevin Y C Lee, Dmitry E Polyansky, David C Grills, James C Fettinger, Marcos Aceves, Louise A Berben

{"title":"Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2.","authors":"Kevin Y C Lee, Dmitry E Polyansky, David C Grills, James C Fettinger, Marcos Aceves, Louise A Berben","doi":"10.1021/acsorginorgau.4c00041","DOIUrl":"10.1021/acsorginorgau.4c00041","url":null,"abstract":"It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemically driven hydride transfer (HT) catalysis. Protonated, air-stable [HFe4N(triethyl phosphine (PEt3))4(CO)8] (H4) was synthesized by reaction of PEt3 with [Fe4N(CO)12]- (A -) in tetrahydrofuran, with addition of benzoic acid to the reaction mixture. The reduction potential of H4 is -1.70 V vs SCE which is 350 mV anodic of the reduction potential for 4 -. Reactivity studies are consistent with HT to CO2 or to H+ (carbonic acid), as the chemical event following ET, when the electrocatalysis is performed under 1 atm of CO2 or N2, respectively. Taken together, the chemical and electrochemical studies of mechanism suggest an ECEC mechanism for the reduction of CO2 to formate or H+ to H2, promoted by H4. This stands in contrast to an ET, two chemical steps, followed by an ET (ECCE) mechanism that is promoted by the less electron rich catalyst A -, since A - must be reduced to A 2- before HA - can be accessed.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"649-657"},"PeriodicalIF":3.3,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621949/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modified Working Electrodes for Organic Electrosynthesis. 用于有机电合成的改良工作电极。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-02 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00050

Alexander C Reidell, Kristen E Pazder, Christopher T LeBarron, Skylar A Stewart, Seyyedamirhossein Hosseini

{"title":"Modified Working Electrodes for Organic Electrosynthesis.","authors":"Alexander C Reidell, Kristen E Pazder, Christopher T LeBarron, Skylar A Stewart, Seyyedamirhossein Hosseini","doi":"10.1021/acsorginorgau.4c00050","DOIUrl":"10.1021/acsorginorgau.4c00050","url":null,"abstract":"Organic electrosynthesis has gained much attention over the last few decades as a promising alternative to traditional synthesis methods. Electrochemical approaches offer numerous advantages over traditional organic synthesis procedures. One of the most interesting aspects of electroorganic synthesis is the ability to tune many parameters to affect the outcome of the reaction of interest. One such parameter is the composition of the working electrode. By changing the electrode material, one can influence the selectivity, product distribution, and rate of organic reactions. In this Review, we describe several electrode materials and modifications with applications in organic electrosynthetic transformations. Included in this discussion are modifications of electrodes with nanoparticles, composite materials, polymers, organic frameworks, and surface-bound mediators. We first discuss the important physicochemical and electrochemical properties of each material. Then, we briefly summarize several relevant examples of each class of electrodes, with the goal of providing readers with a catalog of electrode materials for a wide variety of organic syntheses.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"579-603"},"PeriodicalIF":3.3,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621959/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modified Working Electrodes for Organic Electrosynthesis 用于有机电合成的改良工作电极

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-02 DOI: 10.1021/acsorginorgau.4c0005010.1021/acsorginorgau.4c00050

Alexander C. Reidell, Kristen E. Pazder, Christopher T. LeBarron, Skylar A. Stewart and Seyyedamirhossein Hosseini*,

{"title":"Modified Working Electrodes for Organic Electrosynthesis","authors":"Alexander C. Reidell, Kristen E. Pazder, Christopher T. LeBarron, Skylar A. Stewart and Seyyedamirhossein Hosseini*, ","doi":"10.1021/acsorginorgau.4c0005010.1021/acsorginorgau.4c00050","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00050https://doi.org/10.1021/acsorginorgau.4c00050","url":null,"abstract":"Organic electrosynthesis has gained much attention over the last few decades as a promising alternative to traditional synthesis methods. Electrochemical approaches offer numerous advantages over traditional organic synthesis procedures. One of the most interesting aspects of electroorganic synthesis is the ability to tune many parameters to affect the outcome of the reaction of interest. One such parameter is the composition of the working electrode. By changing the electrode material, one can influence the selectivity, product distribution, and rate of organic reactions. In this Review, we describe several electrode materials and modifications with applications in organic electrosynthetic transformations. Included in this discussion are modifications of electrodes with nanoparticles, composite materials, polymers, organic frameworks, and surface-bound mediators. We first discuss the important physicochemical and electrochemical properties of each material. Then, we briefly summarize several relevant examples of each class of electrodes, with the goal of providing readers with a catalog of electrode materials for a wide variety of organic syntheses.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"579–603 579–603"},"PeriodicalIF":3.3,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring. 扩展五氟苯基n -杂化卟啉的化学性质：反吡咯环外3-C位置的二酮酸取代和衍生化。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-01 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00065

Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw, Chen-Hsiung Hung

{"title":"Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring.","authors":"Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw, Chen-Hsiung Hung","doi":"10.1021/acsorginorgau.4c00065","DOIUrl":"10.1021/acsorginorgau.4c00065","url":null,"abstract":"In this study, we synthesized two new 3-C-substituted pentafluorophenyl-N-confused porphyrins (PFNCPs), one with acetylacetonate (PFNCP-acac, 2a) and the other with ylidene-2-propanone (PFNCP-ac, 3a), through a one-pot reaction in the absence of a catalyst. Under mild acidic and heating conditions, the acac-substituted compound underwent acyl cleavage degradation, yielding ac-substituted product 3a. Subsequent chelation of the acac-substituted PFNCP with BF2 resulted in a boron diketonate derivative, PFNCP-acacBF2 (4). Additionally, an electrocyclic reaction of the ac-substituted PFNCP 3a, without a catalyst, produced a tricyclic fused [6,6,5]-TF-PFNCP (5). This tricyclic product could also be obtained directly from PFNCP-acac 2a under heating conditions. The absorption spectra revealed that acac- and ac-substituted macrocycles exhibit either a single or split Soret band, respectively, in the 400-550 nm range, along with multiple Q bands spanning the 580-690 nm region. While BF2 derivatization caused a slight red shift in the absorption spectra, the [6,6,5]-tricyclic fused NCP demonstrated a significant red shift. All newly synthesized compounds were characterized by using single-crystal X-ray structures, 1H NMR spectroscopy, and mass spectrometry. Density functional theory (DFT) studies were conducted to elucidate the photophysical properties of these macrocycles.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"681-691"},"PeriodicalIF":3.3,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621957/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Study of the BHT Oxidation Mechanism Coupling Theory and Experiment. BHT氧化机理耦合理论与实验研究。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-30 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00067

Edgardo Maximiliano Gavilán-Arriazu, Rubén Darío Alaniz, Patcharawat Charoen-Amornkitt, Juan Manuel Fernández, Gastón Darío Pierini, Sergio Antonio Rodriguez

{"title":"Study of the BHT Oxidation Mechanism Coupling Theory and Experiment.","authors":"Edgardo Maximiliano Gavilán-Arriazu, Rubén Darío Alaniz, Patcharawat Charoen-Amornkitt, Juan Manuel Fernández, Gastón Darío Pierini, Sergio Antonio Rodriguez","doi":"10.1021/acsorginorgau.4c00067","DOIUrl":"10.1021/acsorginorgau.4c00067","url":null,"abstract":"In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pK a and standard oxidation potential (E ox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"692-704"},"PeriodicalIF":3.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621955/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring 扩展五氟苯基n -杂化卟啉的化学性质：反吡咯环外3-C位置的二酮酸取代和衍生化

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-30 DOI: 10.1021/acsorginorgau.4c0006510.1021/acsorginorgau.4c00065

Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw* and Chen-Hsiung Hung*,

{"title":"Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring","authors":"Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw* and Chen-Hsiung Hung*, ","doi":"10.1021/acsorginorgau.4c0006510.1021/acsorginorgau.4c00065","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00065https://doi.org/10.1021/acsorginorgau.4c00065","url":null,"abstract":"In this study, we synthesized two new 3-C-substituted pentafluorophenyl-N-confused porphyrins (PFNCPs), one with acetylacetonate (PFNCP-acac, 2a) and the other with ylidene-2-propanone (PFNCP-ac, 3a), through a one-pot reaction in the absence of a catalyst. Under mild acidic and heating conditions, the acac-substituted compound underwent acyl cleavage degradation, yielding ac-substituted product 3a. Subsequent chelation of the acac-substituted PFNCP with BF2 resulted in a boron diketonate derivative, PFNCP-acacBF2 (4). Additionally, an electrocyclic reaction of the ac-substituted PFNCP 3a, without a catalyst, produced a tricyclic fused [6,6,5]-TF-PFNCP (5). This tricyclic product could also be obtained directly from PFNCP-acac 2a under heating conditions. The absorption spectra revealed that acac- and ac-substituted macrocycles exhibit either a single or split Soret band, respectively, in the 400–550 nm range, along with multiple Q bands spanning the 580–690 nm region. While BF2 derivatization caused a slight red shift in the absorption spectra, the [6,6,5]-tricyclic fused NCP demonstrated a significant red shift. All newly synthesized compounds were characterized by using single-crystal X-ray structures, 1H NMR spectroscopy, and mass spectrometry. Density functional theory (DFT) studies were conducted to elucidate the photophysical properties of these macrocycles.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"681–691 681–691"},"PeriodicalIF":3.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00065","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760847","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Study of the BHT Oxidation Mechanism Coupling Theory and Experiment BHT氧化机理耦合理论与实验研究

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-29 DOI: 10.1021/acsorginorgau.4c0006710.1021/acsorginorgau.4c00067

Edgardo Maximiliano Gavilán-Arriazu*, Rubén Darío Alaniz, Patcharawat Charoen-amornkitt, Juan Manuel Fernández, Gastón Darío Pierini and Sergio Antonio Rodriguez*,

{"title":"Study of the BHT Oxidation Mechanism Coupling Theory and Experiment","authors":"Edgardo Maximiliano Gavilán-Arriazu*, Rubén Darío Alaniz, Patcharawat Charoen-amornkitt, Juan Manuel Fernández, Gastón Darío Pierini and Sergio Antonio Rodriguez*, ","doi":"10.1021/acsorginorgau.4c0006710.1021/acsorginorgau.4c00067","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00067https://doi.org/10.1021/acsorginorgau.4c00067","url":null,"abstract":"In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"692–704 692–704"},"PeriodicalIF":3.3,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00067","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0